3ia 


EXCHANGE 


Synthesis    of    2-methyl-4-selenoquinazolone, 

2-phenylbenzoselenazole,  and  Its 

Derivatives. 


DISSERTATION 


SUBMITTED  IN  PARTIAL  FULFILLMENT  OF  THE  RE- 
QUIREMENTS FOR  THE  DEGREE  OF  DOCTOR  OF 
PHILOSOPHY  IN  THE   FACULTY  OF  PURE 
SCIENCE   OF  COLUMBIA  UNIVERSITY 


BY 

YU-GWAN  CHEN,  M.  A. 

NEW  YORK  CITY 
1922 


Synthesis    of    2-methyl-4-selenoquinazolone, 

2-phenylbenzoselenazole,  and  Its 

Derivatives. 


DISSERTATION 


SUBMITTED  IN  PARTIAL  FULFILLMENT  OF  THE  RE- 
QUIREMENTS FOR  THE  DEGREE  OF  DOCTOR  OF 
PHILOSOPHY  IN  THE  FACULTY  OF  PURE 
SCIENCE   OF  COLUMBIA  UNIVERSITY 


BY 

YU-GWAN  CHEN,  M.  A. 

NEW  YORK  CITY 
1922 


0A 


ACKNOWLEDGMENT  AND  DEDICATION 

The  following  research  was  undertaken  at  the  suggestion  of 
Professor  Marston  Taylor  Bogert  to  whose  interest  and  advice 
this  work  owes  whatever  merit  it  may  possess. 

Y.  G.  CHEN. 


CONTENTS 

Acknowledgment  and  Dedication 2 

Abstract  of  the   Dissertation 4 

Purpose  of  the  Research 5 

Introduction    7 

Pharmacological   Review    8 

Tinctorial    Review 14 

Experimental :    16 

2-methyl-4-selenoquinazolone 

Four  Methods  of  Preparation 

Analysis  of  Selenium  Organic  Compounds 

2-phenylbenzoselenazole 

Mononitro  Derivative 

Monoamino  Derivative 

Monoacetyl  Derivative 

Monobenzylidene  Derivative 

An  Azo  Dye 

Dinitro  Derivative 

Diamino  Derivative 

Diacetyl  and  Dibenzylidene  Derivatives 
Dyeing  with  Azo  Dyes 

Bibliography  25 

Vita  .  28 


3  478711 


ABSTRACT  OF  THE  DISSERTATION 

1 .  What  was  attempted  ? 

Attempt  was  made  to  study  organic  selenium  compounds  of 
the  heterocyclic  series  in  reference  to  those  properties  leading 
to  tinctorial  and  pharmaceutical  possibilities. 

2.  What  were  the  methods  of  attack? 

(a)  Organic  selenium  compounds  were  reviewed  and  their 
properties  examined  critically  with  those  of  allied  compounds. 

(b)  Some  new  heterocyclic  compounds  of  selenium  were 
studied  and  their  characteristic  properties  more  closely  examined 
along  the  desired  line. 

3.  In  how  far  were  the  attempts  successful? 

The  literature  was  reviewed  and  classified  with  reference  to 
the  properties  under  consideration,  and  new  selenium  organic  com- 
pounds were  prepared  and  studied  which  it  is  hoped  may  throw 
some  additional  light  upon  the  problem. 

4.  What  contribution  actually  new  to  the  science  of  chemistry 
has  been  made? 

(a)  Compounds  newly  made  have  been  shown  to  exhibit  a 
distinct  tinctorial  value  in  comparison  with  their  analogues. 

(b)  They  have  been  shown  to  be  chemically  easier  to  handle 
than  the  corresponding  sulphur  compounds. 

(c)  Selenium,  in  the  nucleus  of  cyclic  compounds,  has  been 
shown  to  be  instrumental  for  a  positive  coloration  at  least  equal 
to  the  — NH —  or  — S —  groupings.    The  selenocarbonyl,  :C  :Se, 
ha,s  been  shown  to  be  a  more  powerful  chromophore  than  thio- 
carbonyl,   :C:S,  or  carbonyl  itself,   :C:O. 

(d)  Two  series  of  azo  dyes  of  selenium  have  been  prepared 
and  have  been  shown  to  possess  a  marked  tinctorial  value. 

(e)  The  following  new  compounds  have  been  prepared : 
2-methyl-4-selenoquinazolone 
2-phenylbenzoselenazole* 
6-nitro-2-phenylbenzoselenazole 
6-amino-2-phenylbenzoselenazole 
6-acetylamino-2-phenylbenzoselenazole 
6-benzylideneamino-2-phenylbenzoselenazole 
(B-naphthyl)-6-azo- (2-phenylbenzoselenazole) 
Dinitro-2-phenylbenzoselenazole 
Diamino-2-phenylbenzoselenazole 
Diacetyldiamino-2-phenylbenzoselenazole 
Dibenzylidenediamino-2-phenylbenzoselenazole 

*  Not  a  new  compound  but  prepared  by  a,  different  method. 

4 


PURPOSE  OF  THE  RESEARCH 

Since  Berzelius  published  the  first  resume  of  the  chemistry 
of  selenium,  in  1818  (*),  many  articles  have  appeared  in  this 
field.  Several  reviews  (2)  of  its  compounds,  including  references, 
have  been  published,  besides  the  resumes  in  the  chemical  diction- 
aries. These  reviews  are  confined  mainly  to  the  inorganic  side. 
No  attempt  has  ever  been  made  to  compile  a  bibliography  of 
selenium  organic  compounds. 

From  time  to  time,  articles  have  appeared,  but  the  field  is 
still  a  promising  one,  with  many  alluring  possibilities. 

In  the  perusal  of  the  organic  records  of  the  metal,  distributed 
over  the  span  of  a  century,  there  are  indications  of  the  value  of 
selenium  compounds  for  pharmaceutical  and  tinctorial  uses. 
An  effort  has  been  made  to  collect  these  scattered  data  for  crit- 
ical examination  with  other  analogues  and  sulphur  compounds 
in  particular,  and  to  prepare  and  study  some  new  organic  com- 
pounds containing  selenium,  for  the  purpose  of  gaining  addi- 
tional light  upon  the  chemistry  of  such  substances,  and  in  the 
hope  of  discovering  some  which  may  be  of  practical  service 
in  medicine  or  elsewhere. 


Synthesis  of  2-methyl-4-selenoquinalozone, 

2-phenylbenzoselenazole  and  Its 

Derivatives 


INTRODUCTION       . 

The  general  conception  of  selenium  is  that  it  is  a  compara- 
tively rare  element.  Few  realize  that  it  has  been  known  for 
over  a  century  and  that  over  twenty  selenium  minerals,  contain- 
ing from  one  to  sixty-six  per  cent,  of  the  metal,  are  considered  by 
the  mining  corporations  as  important.  Beside  being  a  by- 
product of  sulphuric  acid  manufacture,  it  is  separated  also  in  the 
electrolytic  refining  of  copper.  The  demand  for  the  metal  is  so 
small  that  there  are  half  a  dozen  concerns  in  the  United  States 
either  willing  to  supply  gratis  any  reasonable  quantity  for  re- 
search work,  or  to  sell  it  at  cost.  In  a  special  report  of  the 
National  Research  Council  on  selenium  (3),  it  is  estimated  that 
there  could  be  produced  annually,  without  making  any  material 
additions  to  the  present  plants,  not  less  than  300,000  pounds. 

In  fact  selenium  has,  in  recent  years,  gradually  been  brought 
more  and  more  to  the  attention  of  the  general  public  through 
its  application'  to  military  uses  and  other  purposes.  In  the  glass 
industry,  for  example,  it  was  used  as  decolorizer  during  the 
War  period.  It  has  been  found  that  it  imparts  a  violet  red  tint 
to  the  pyrex  tubing  after  the  latter  has  been  used  for  a  few  com- 
bustions. The  coloration  is  especially  noticeable  when  a  broken 
piece  is  examined.  This  may  find  an  important  place  in  the 
ceramic  industry.  In  turning  off  the  gas  light  of  the  city  at 
day  break,  in  controlling  the  draft  of  the  factory  chimneys,  and 
in  regulating  the  rapidity  of  the  manufacture  of  sulphuric  acid, 
the  selenium  cell  is  an  important  labor  saving  factor.  In  a 
similar  way  it  is  used  in  automatically  lighting  and  extinguish- 
ing light  buoys.  It  also  finds  application  in  photometry,  wireless 
telephony,  military  telegraphy,  and  army  signaling  as  well  as 
for  the  transmission  of  signatures,,  handwritings,  finger  prints, 
and  images  in  general  (?-,  4). 

The  question  of  the  vulcanization  of  rubber  also  should  be 
considered.  Some  experiments  have  been  published  claiming  the 
similarity  of  the  action  of  selenium  and  sulphur  on  rubber  (4,  5). 
The  cost  need  not  be  prohibitive,  since  the  supply  could  be 
easily  increased  and  the  price  reduced  provided  there  were  .a 
demand.  In  the  personal  experience  of  the  writer,  when  work- 
ing with  the  hydrogen  selenide  gas,  the  rubber  connections  of 
the  apparatus  soon  turned  red,  and  after  a  few  hours  were  so 


clear  a  red  that  visitors  to  the  laboratory  imagined  that  the  writer 
was  using  the  ordinary  red  rubber  connections.  The  rubber 
thus  changed  seems  to  be  softer  and  more  elastic  than  the 
original ;  this  observation  will  be  followed  up. 

In  this  country  the  National  Research  Council  has  created 
a  special  committee  of  seven  to  investigate  the  various  possible 
uses  of  selenium  and  tellurium. 

PHARMACOLOGICAL   REVIEW 

Duhamel  and  Rebiere  (6,  7)  showed  that  an  injection  of  a 
trace  of  red  colloidal  selenium  into  rabbits  increased  urea  ex- 
cretion regularly.  In  other  cases  satisfactory  results  were  claimed 
and  the  liver  showed  some  lesions.  The  histological  modifica- 
tions produced  by  injections  into  rabbits  are  most  apparent 
in  the  liver  and  kidneys.  In  the  distribution  of  colloidal  prep- 
arations in  the  animal  body  by  injection,  Duhamel  and  Juillard 
(8)  found  that  the  liver  contained  the  greatest  amount.  Six 
years  later  the  former  (9)  used  a  similar  preparation  introduced 
into  the  animal  intravenously,  and  selenium  was  again  found 
in  the  liver,  although  in  smaller  quantity. 

Sulphur  compounds  have  similar  physiological  action.  It 
is  known  that  triphenylstibine  sulphide,  or  sulphoform,- 
(C6H5)3SbS,  has  a  curative  effect  in  skin  diseases,  as  it  liberates 
"nascent"  sulphur  on1  the  skin.  It  is  equally  natural  to  expect 
some  organic  selenium  compound  which  liberates  finely  divided 
selenium  to  exert  a  remedial  influence  on  animal  bodies.  The 
selnoquinazolone  prepared  in  the  course  of  this  research  and  de- 
scribed more  fully  in  another  section  of  the  paper,  has  this  pros- 
pect. The  quinazolone  has  the  following-  structure: 


Experiments  were  carried  on  at  L'Institut  Pasteur  in  Paris 
under  the  supervision  of  M.  Borel  for  the  treatment  of  cancer  in 
mice.  No  human  subjects  were  experimented  upon,  although  re- 
sults were  claimed  by  using  selenides  and  their  oxidized  salts. 

Selenium  dyes  were  found  to  be  medicinals,  although  no 
relation  has  yet  been  established  between  constitution  of  these 
organic  dyes  and  their  therapeutic  value.  Wassermann  (10)  made 
several  eosin  preparations,  by  coupling  the  sodium  derivative 
with  potassium  selenocyanidc.  The  red  dyestuf?  thus  prepared 
is  stated  to  be  easily  soluble  in  water.  Wassermann,  Keysser 
and  Wassermann  (")  made  experiments  with  it,  chemothera- 
peutically,  on  animal  tumors.  When  the  solution  was  injected 

8 


into  mice  tumors  the  latter  turned  red,  accompanied  by  the  soft- 
ening- of  the  tumor  after  the  third  injection  and  complete  resorp- 
lion  after  ten  injections,  unless  the  dose  used  was  too  great  for 
the  animal.  In  that  case  death  often  occurred.  Good  results 
were  also  reported,  in  connection  with  this  experiment,  on  four 
different  strains  of  mouse  carcenoma  and  one  strain  of  mouse 
sarcoma.  In  the  latter  case,  relief  was  found  sooner  but  the 
former  disappeared  more  slowly.  Another  preparation  was  made 
later  (12)  and  introduced  into  mice  intravenously  and  again  found 
to  have  good  results. 

The   following  is   the   structure   of  2-selenocyanideanthra- 
quinone — 


SeCN 


which  has  also  been  reported  to  have  medicinal  uses  (13) 

P.  Ehrlich  and  Hugo  Bauer  (14)  synthesized  from  p.p'- 
diamino-diphenyl-methane  the  red  dye  3,  6-diaminoseleno- 
pyronine. 


NH2 


The  dye  has  been  used  upon  mice  and  caused  pronounced  edema. 
The  toxicity  of  both  the  selenopyronine  and  the  corresponding 
sulphur  compound  was  compared  under  similar  conditions  in 
the  same  experiment,  and  it  was  found  that  the  selenium  dye  was 
toxic  in  1/3000  gram,  but  the  sulphur  dye  was  toxic  in  1/2500 
gram  per  twenty  gram  weight  of  the  animal. 

This  physiological  activity  was  noted  years  ago  with  the 
inorganic  compounds  of  selenium  and  Berzelius  (15)  described 
the  poisonous  effect  of  hydrogen  selenide  quite  impressively; 
"In  order  ta  get  acquainted  with  the  smell  of  this  gas  I  allowed 
a  bubble  not  larger  than  a  pea  to  pass  into  my  nostril ;  in  conse- 
quence of  its  smell  I  so  completely  loss  my  sense  of  smell  for 
several  hours  that  I  could  not  distinguish  the  odor  of  strong 
ammonia  even  when  held  under  my  nose.  My  sense  of  smell 
returned  after  five  or  six  hours,  but  severe  irritation  of  the 
mucous  membrane  set  in  and  persisted  for  a  fortnight/'  The 
writer  has  been  working  on  the  gas  for  some  time  and  was 
also  quite  seriously  affected  once,  the  injury  persisting  for  many 

9 


days.  That  it  is  more  poisonous  than  the  hydrogen  sulphide  is 
well  known. 

Bruere  (16)  showed  that  when  hydrogen  sulphide  was  passed 
into  blood  solution  sulphemoglobin  was  produced  in  considerable 
quantity,  due  to  the  chemical  action  of  sulphur  and  hematin.  He 
stated  further  that  sulphemoglobin  may  be  found  in  animal  blood 
when  a  large  amount  of  the  gas  has  been  inhaled.  He  made 
selenhemoglobin  in  the  same  manner.  Sixteen  years  later,  Clarke 
and  Hartley  also  proved  that  selenhemoglobin  may  be  made  by 
passing  hydrogen  selenide  into  blood  (17).  These  experiments 
may  be  interpreted  to  mean  that  the  oxy-hemoglobin  is  trans- 
formed into  an  organic  complex  of  sulphur  or  selenium,  an(l  that 
the  transference  may  be  more  rapid  and  powerful  in  the  case  of 
hydrogen  selenide. 

Biological  investigations  have  sufficiently  proved  that  dye- 
stuffs  of  the  phenazine,  oxasine,  thiazine,  acridine  series  show 
an  injurious  effect  on  protozoa,  especially  those  dyes  containing 
substituted  amino  groupings  and  of  a  simple  structure  (18).  In 
the  case  of  the  thiazine  dyes  of  the  methylene  blue  class,  the 
physiological  importance  has  well  recognized  in  their  use  as 
feeble  antiseptics  and  analgesics.  Ehrlich  and  Guttmann  (10) 
initiated  the  use  of  methylene  blue  as  an  antiperiodic  and  its 
use  in  that  line  has  been  continued. 

In  the  field  of  the  selenazine  dyes,  pharmacologists  have  not 
yet  paid  much  attention  to  them,  on  account  of  the  newness  of 
the  discovery,  but  P.  Karrer  claims  that  they  are  indisputably 
"vital  dyestuffs"  (20).  The  prospect  of  synthesizing  selenazine 
dyes  and  their  use  as  drugs  seems  to  be  bright,  judging  from  the 
fact  that  they  are  easily  prepared  and  capable  of  many  com- 
binations, especially  of  the  ease  with  which  they  form  organic 
complexes  with  arsenic  compounds. 


Formula  (I)  is  known  as  1,  3-dinitrobenzoselenazine  (21),  which 
was  obtained  by  the  action  of  picryl  chloride  pn  the  zinc  salt 
of  o-aminoselenophenol  ;  the  product  (picrylaminoselenophenol) 
being  then  treated  with  alkali  and  thus  converted  to  the  dye, 
which  upon  experimentation  showed  marked  effects  upon  proto- 
zoa and  bacteria. 


10 


H03As 


H03As 


Formula  (II),  known  as  3-(p-phenylarsonic)-aminoselenazine, 
is  red  in  dilute  alkali  and  green  in  mineral  acid,  and  is  a  typical 
dye  in  a  series  from  the  coupling  of  selenodiphenylamine  with 
arsenic  compounds.  All  possess  similar  toxicity  as  the  thiazine 
dyes  (20).  Other  selenazines  are  listed  in  the  bibliography  (22). 

No  less  than  half  dozen  thioureas  are  commonly  used  as 
drugs.  Thiourea  itself  paralyzes  the  nerve  centers,  and  is  em- 
ployed commercially  for  photograph  fixing  and  for  removing 
stains  from  negatives;  thiuret,  C6H'7N3S2,  serves  as  a  substitute 
for  iodoform';  thiosinamine-ethyliodide,  or  tiodine,  IH5C2H<2- 
NCSNHC3H5,  is  used  for  relief  of  lesions  of  the  central  nervous 
system;  allylthiourea  or  thiosinamine,  (NH'2)SC.NHCHj2CH:- 
CH2,  for  aiding  the  absorption  of  connective  tissues,  for  treat- 
ment of  burns,  keloids,  urethral  diseases,  sclerotic  conditions  of 
the  ear  (23). 

Selenocarbamide  and  a  number  of  its  derivatives  have  been 
prepared  and  studied.  One  class  of  seleno  ureas  has  been 
patented  as  pharmaceutical  products  by  Chem.  Fabrik  von  Hey- 
den  (24),  and  are  prepared  by  the  action  of  hydrogen  selenide 
on  a,lkylcyanamides, 

RNH.CHN  +  H2Se  =  RNH.CSe.NH2 

They  possess  pronounced  therapeutic  value  and,  serve  as  inter- 
mediate products  in  the  production  of  more  stable  alkyl  halide 
additive  compounds.  Other  carbamides  ranging  from  seleno 
urea  itself  (25),  (III)  and  a  cyclic  urea  (28)  (IV)  are  described 
in  the  literature: 


NH2 


The  latter,  known  as  ethylene-selenourea,  may  be  classified  also 
in  the  azole  group  as  2-iminotetrahydroselenazole  (V). 


11 


H2C  — NJH 


C:NH 


The  literature  for  the  other  normal  carbamides  is  listed  in  the 
bibliography  (27). 

Selenoantipyrines,  selenosaccharine,  selenoindigoes  have 
also  been  prepared. 

Thiophene  and  its  derivatives  are  of  considerable  therapeutic 
interest.  Thiophene  itself  is  found  to  be  useful  in  lessening  the 
elimination  of  sulphuric  acid  in  urine,  and  is  employed  in  the 
dermatological  practice.  Sodium  thiophene  sulphonate,  thio- 
phenetetra-bromide,  thiophene  diiodide,  are  all  medicinals  (23). 

A  number  of  selenophenes  are  recorded  in  the  literature. 
Their  relation  to  the  selenazoles  may  be  easily  seen  from  the 
following  formulas: 


CH 


CH 
\ 


CH 


CH 


CH — N 


5e 

Selenophene 


CH        CH 

v 

Selenazole 


Dimethyl  selenophene  was  prepared  from  acetonyl  acetone 
and  phosphorous  pentaselenide, 


HC— C 


XOH 


NCH 


HC=C, 

HC  =  £ 


'Se 


CH 


The  compound  thus  obtained  is  stated  to  have  the  same  odor 
as  thiophene,  but  no  mention  is  made  In  regard  to  its  uses  (28). 
Selenophene  was  prepared  from  sodium  succinate  and  phos- 
phorous triselenide,  or  by  conducting  ethylselenide  through  hot 
tubes  (29). 

Some  selenazoles  find  application  also  in  medicine.  At  pres- 
ent only  the  isoazoles  are  known  to  have  physiological  uses.  One 
of  them  was  prepared  from  anthraquinone  selenocyanide,  by  the 
action  of  ammonia  under  pressure  (30). 

12 


HCN 


Another  type  of  azoles,  benzoselendiazole  (piaselenol)  and  five 
of  its  derivatives,  have  been  also  described  as  medicinals  (31). 
The  diazole  itself  has  the  following  structure, 


Diazoles  of  the  following  structure  are  also  known,  but  no 
data  were  found,  regarding  their  physiological  action  (32)  : 


Se 

Dimethyl-seleno-  Diphenyl-seleno- 

diazole  diazole 

Sulphides  and  disulphides  have  curative  power.  Dimethyl- 
sulphide  is  used  for  internal)  treatment,  di-o-aminophenyldi- 
sulphide  is  used  for  intramuscular  injections.  Diallyl  sulphide 
is  also  a  medicament.  Methyl  selenide  has  some  effect  on  the 
internal  parts  of  the  body  (33).  Hanzlik  and  Tarr  (34)  at  the 
American  University  Experimental  Station,  showed  that  a  num- 
ber of  selenium  compounds  act  as  skin  irritants :  e.g.,  dichloro- 
diethyl  selenide,  dichlorovinyl  selenide,  trichlorodiethyl  selenide 
and  selenium  mustard  oil.  The  first  mentioned  proved  as  potent 
as  the  sulphide,  but  the  others  fell  somewhat  below  in  their  effects. 
Diantipyryl  selenide  is  another  therapeutical  agent  (8B). 

The  diselenides  occupy  an  important  place  of  their  own. 
The  selenophenols  do  not  remain  unchanged  in  the  air,  but  are 
always  oxidized  to  the  diselenides,  which  can  be  again  reduced 
to  the  selenophenols.  So  far  only  the  diselenides  of  anthra- 
quinone  and  their  phenols  are  recognized  remedies  (36). 


13 


TINCTORIAL  REVIEW 

Many  of  the  seleno  organic  compounds  are  colored,  while 
the  corresponding  sulphur  derivatives  are  colorless. 

HC-CH  HC-CH 

II          H  II  If 

HC\o/H  H 

Furane,     color-lets  Thiophene,    colorless 

liquid  liquid 

HC  —  CH  HC  —  CH    ? 

«  H  If  (I 

HC       CH  HC         CH 

\       /  \      / 

NH  5* 

Pyrrol,    colorless    liq.  Selenophene,    yellow    liq. 

but  turns  brownish   in  air  after    repeated    extraction 

This  brings  selenophene  more  akin  to  pyrrole  than  thiophene,  but 
the  group  -NH-  in  the  molecule  of  pyrrole  is  an  auxochrome., 
The  selenium  atom  in  a  cyclic  compound  also  acts  like  an 
auxochrome. 

Selenoantipyrine  (37), 

C6HS 


CH,N  CSe 

1  1 


forms  pure  yellow  crystals  from  alcohol,  while  the  corresponding 
compounds  of  oxygen  and  sulphur  are  colorless. 

Similarly,  the  2-methyl-4-selenoquinazolone  is  deep  brown 
in  color,  while  the  thio  compound,  prepared  by  Bogert  and  Hand 
(38)  is  light  brown  or  yellow  and  the  corresponding  oxygen 
compound  is  colorless  or  nearly  so. 

Diethyl  selenide  (C2H5)2Se,  is  a  yellowish  heavy  oil  of  un- 
pleasant odor.  It  combines  readily  with  chlorine  to  form  a 
chloride  (C2H5)2SeCl2,  and  the  latter  is  oxidized  by  nitric  acid  to 
form  an  oxide  (C2H5)2SeO,  (39).  Diethyl  sulphide  is  a  colorless 
syrupy  liquid,  as  well  as  diethyl  amine  and  diethyl  ether. 

The  gradation  of  color  is  quite  pronounced  in  the  case  of 
selenonaphthene  quinone  (40). 

*  Note  —  dimethyl   selenophene,    however,    is   colorless. 

14 


It  would  be  most  natural  to  conclude  that  the  chromophore  :CS 
is  more  powerful  than  -CO,  and  that  :CSe  is  most  powerful  of 
all,  as  shown  in  our  study  of  quinazoline  compounds.  It  would 
equally  follow  that  :S  is  a  more  powerful  color-forming  radical 
in  a  cyclic  compound  than  that  of  :O ;  and  :NH  than  that  of 
:S ;  and  Se  again  most  powerful  of  the  whole  series. 

Lesser  and  Weiss  (41)  in  their  research  on  selenoindigo 
stated  that  the  selenium  dyestuff,  on  account  of  its  greater  mole- 
cular weight  than  sulphur,  shows  a  deeper  blue.  This  hypothesis 
meets  a  difficulty  in  the  case  of  coumora,ndione,  thionaphthene- 
quinone  and  isatin  series,  where  the  -NH-  radical  has  an  atomic 
weight  of  15,  and  -S-  32,  and  showed  the  reversed  order  of  color. 
This  seems  to  be  the  case  in  the  selenophene  series  also.  There- 
fore this  theory  is  not  without  exceptions. 

The  diselenides  present  a  very  interesting  study  also. 
Methyl  disulphide  is  colorless,  but  methyldiselenide  (42)  is  a 
reddish  yellow  liquid.  Mtethyl  disulphide  only  becomes  yellow 
when  it  is  treated  with  chlorine,  and  in  such  cases  (GH:{)2S2CL> 
is  formed  (i3),  in  yellow  rhombic  crystals.  Ethyldisulphide  is 
colorless;  ethyldisulphidedichloride  is  a  faint  yellow  oil  (44). 
But  the  corresponding  ethyldiselenide  is  a  red  liquid  (45).  Phenyl 
disulphide  is  colorless,  and  phenyldisulphide  dibromide  is  of 
mother-of-pearl  appearance,  and  practically  colorless  (46),  while 
phenyl  diselenide  forms  pure  yellow  needles  (47),  and  phenyl- 
diselenide  dibromide  orange  red  ones. 

While  phenyldisulphide  is  colorless,  when  an  auxochrome 
group  is  added,  such  as  NH;,M  the  compound  is  colored.  This  is 
the  case  with  o-diaminodiphenyldisulphide  (48)  which  is  yellow 
both  in  solution  and  in  crystalline  form.  In  other  words,  an  auxo- 
chrome in  addition  to  the  chromophore  group  transforms  a  col- 
orless chromoo-en  into  a  colored  one.  Therefore  groups  like 
-S.S-  and  -Se.Se-  are  chromophores  in  the  same  sense  as  -N:N-. 
This  is  in  agreement  with  the  chromophore  ideas  of  Hugo  Kauf- 
mann.  The  -Se.Se-  is  a  more  powerful  .chromophore  than 
-S.S-. 

This  brings  one  directly  to  the  inquiry  as  to  why  2-phenyl- 
benzoselenazole,  which  contains  a  :Se  radical,  should  be  color- 
less; and  that  even  6-nitro-2-phenylselenazole,  with  the  addition 
of  a  chromophore  NO2,  should  be  only  faintly  colored.  The 
benzothiazoles,  their  isomers  and  derivatives  are  mostly  color- 
less, and  similar  causes  are  probably  responsible  in  the  case  of  the 
phenylbenzoselenazole,  for  its  lack  of  color.  But  when  this 

15 


selenazole  is  combined  with  another  chromophore,  for  example 
an  azomethine  grouping,  the  result  is  a  more  positively  colored 
compound  (in  this  case  benzalaminoselenazole),  the  crystals 
being  yellow.  The  corresponding  thiazole  derivative  is  light 
colored. 

The  tinctorial  value  of  the  selenium  derivative  is  further 
evidenced  by  the  ease  with  which  it  forms  azo  dyes  and  the  deep 
colors  of  the  latter.  This  was  observed  when  6-amino-2- 
phenylbenzoselenazole  was  diazotized  and  coupled  with  B-naphthol, 
salicylic  acid,  etc.  The  corresponding  aminothiazole  has  been  con- 
sidered difficult  to  diazotize,  on  account  of  its  insolubility  in  hydro- 
chloric acid,  cold  or  hot,  but  the  aminoselenazole  dissolves  readily 
and  completely,  the  coupling  is  almost  instantaneous,  and  the  dyes 
obtained  a,re  mostly  red  and  of  metallic  lustre.  In  view  of  the 
stability  of  benzoselenazoles  toward  hot  concentrated  acids  (with 
the  exception  of  nitric,  when  nitration  ensues)  and  alkalis,  these 
dyes  may  prove  of  some  commercial  interest. 

The  azole  dyes  of  the  benzoselenazole  have  been  exposed  to 
light  for  weeks,  and  also  exposed  to  acids  and  alkalis,  and  have 
been  found  to  be  quite  fast. 


EXPERIMENTAL 


Preparation  of  2-methyl-4-selenoquinazolone 
Busch  prepared  quinazolines  by  the  action  of  o-amino  or 
o-nitro  benzylamine  with  phosgene,  and  thioquinazolines  with 
carbon  disulphide  (51)  : 


yCH2-NH 

COC17        -      C,H/  | 

NNH-co 


C52 


Accordingly  the  same  reaction  was  tried  with  o-nitrobenzyl- 
amine,  prepared  by  the  method  of  Lellmann  and  S'tickel  (50), 
using  carbon  diselenide  (51).  The  reaction  seemed  to  work,  but 
the  mixture  formed  was  difficult  to  extract  and  it  appeared  that 
other  reactions  took  place  at  the  same  time,  due  to  the  impurity 
of  the  carbon  diselenide,  as  the  latter  has  never  been  prepared 
in  the  pure  state. 

Another  method,  which  is  equally  attractive  because  of  its 
simplicity,  is  that  of  Babriel  and  Stelzner  (52), 

16 


XCHO  NH2  /CH-N  H20 

C6VU  +  i  CbH^  1         4- 

^NHZ  HZN-CO  ^N  H-CO         NH3 

Tn  accordance  with  the  above  reaction  o-aminobenzaldehyde 
should  work  with  equal  ease  with  selenocarbamide,  but  the  initial 
materials  were  not  available. 

The    reaction    which    was    used    successfully    was    that    of 
Bogert,  Breneman  and  Hand  (53), 

NH 


NCS-NHZ  \CS-NH 

+  or 

H5  N 


/NHCOfc.  SH 

0   ->  CtH/ 

NCN 

The  hydrogen  selenide  used  in  the  reaction  was  prepared  from 
FeSe  by  the  action  of  hydrochloric  acid,  or  by  heating  paraffin  and 
selenium,  in  the  proportion  of  four  to  one  respectively,  at  335° 
to  350°C  (54). 

The  selenoquinazoline  was  prepared  from  anthranilic  nitrile 
by  the  following  methods  —  the  anthranilic  nitrile  being  prepared 
from  o-nitraniline  (57), 

(a)  20  grams  of  acetyl-anthranilic  nitrile  was  dissolved  in 
absolute  alcohol,  and  dry  hydrogen  selenide  and  dry  ammonia 
passed  into  the  solution  for  three  hours.    The  quinazoline  crystal- 
lized out  gradually  on  cooling  was  filtered  out  and  recrystajized 
from  dilute  alcohol.     The  yield  was  about  ten  per  cent. 

(b)  10   grams    of   acetyl-anthranilic   nitrile   was   heated    in 
a  sealed  tube  at  110°  with  alcohol  saturated  at  zero  degree  with 
dry  hydrogen  selenide  and  dry  ammonia.     After  five  hours,  the 
tube  was  taken  out  and  the  quinazoline  crystallized  out  on  cool- 
ing.   Yield  was  about  sixteen  per  cent. 

As  hydrogen  selenide  was  somewhat  unstable  and  did  not  dis- 
solve freely  in  alcohol,  freshly  prepared  sodium  selenide  was 
used  in  the  following  method  and  was  found  to  be  more  satis- 
factory. It  was  prepared  from  Sodium  hydroxide  in  absolute 
alcohol  by  passing  dry  hydrogen  selenide  into  the  solution  for 
about  three  hours.  In  the  beginning  and  end  of  the  reaction, 
nitrogen  was  used  to  exclude  the  oxyggn  of  the  air.  The  selenide 
was  collected  and  dried  in  an  atmosphere  of  nitrogen,  and  then 
in  a  vacuum,  in  presence  of  phosphorus  pentoxide.  When  thus 
prepared,  sodium  selenide  was  colorless,  but  on  exposure  to 

17 


air  it  turns  reddish  and  finally  dark  colored.  The  C.  P.  selenide 
on  the  market  was  black  and  was  found  to  be  entirely  useless. 

(c)  20  grams  of  anthranilic  nitrile  and  fifty  grams  of  sodium 
selenide  were  mixed  and  heated  in  a  distilling  flask  in  an  at- 
mosphere of  nitrogen,  and  forty  grams  of  acetic  anhydride  drop- 
ped into  the  flask  very  slowly.     The  temperature  was  kept  at 
115°  for  half  an  hour  and  then  raised  to  distill  off  the  acetic  acid 
termed  in  the  reaction,  as  the  condensation  hardly  went  to  com- 
pletion in  the  presence  of  any  trace  of  acetic  acid.   The  whole  pro- 
cess took  an  hour  and  half.    The  flask  was  removed  from  the  oil 
bath  and,  after  cooling,  dilute  alkali  was  run  in,  in  successive  por- 
tions, to  dissolve  out  the  quinazoline.     Into  the  clear  alkaline 
extracts  carbon  dioxide  was  bubbled  for  an  hour,  and  common 
salt  then  added.     The  precipitrate  was  recrystallized  several  times 
from  twenty-five  per  cent,  alcohol.    The  yield  was  from  twenty 
to  twenty-five  per  cent. 

(d)  10  grams  of  anthranilic  nitrile,  twenty  grams  of  acetic 
anhydride,  and  twenty-five  grams  of  sodium  selenide  were  mixed 
in  a  sealed  tube  and  heated  together  for  three  hours  and  half  at 
110°-115°.     The   condensation   product   wa,s   crystalline   when   the 
tube  was   cooled  to  room   temperature.     The   contents   of   the 
tube  were  extracted  with  dilute  alkali  as  before,  filtered,  preci- 
pitated by  carbon  dioxide,  and  recrystallized  from  dilute  alcohol. 
The  yield  was  not  over  twenty  per  cent. 

(e)  An  attempt  was  made  to  make  o-aminobenzselenamicle, 
and  from  the  latter,  by  treatment  with  acetic  anhydride,  to  form 
the  quinazoline,  but  the  yield  of  the  amide  was  too  small  to 
carry  the  reaction  further. 

The  substance  prepared  by  the  above  methods  crystallizes 
from  dilute  alcohol  in  needles  or  prisms  of  dark  brown  color. 
It  melts  at  213.5°  (corr.).  It  dissolves  readily  in  hot  alcohol  but 
on  concentration  sometimes  forms  a  sticky  mass  with  a  peculiar 
but  not  unpleasant  odor.  It  dissolves  readily  in  alkalies  a,nd  is 
slightly  soluble  in  hot  benzene  and  chloroform,  but  insoluble 
in  hot  water.  Crystals  purified  from  (a)  were  analyzed  and 
gave  the  following  results : 

Calculated  for  Found 

C0H8N2Se  I  II 

Carbon 48.38%  48.45%  48.62% 

Hydrogen    ....  3.61  3.82  3.52 

Nitrogen    12.55  12.51  12.66 

Selenium    ....  35.46  35.60  35.42 

The  crystals  on  standing  in  the  presence  of  air  and  light  de- 
composed with  separation  of  finely  divided  selenium  and  methyl 
quinazolone. 

Analysis  of  Selenium  Organic  Compounds 

In  the  quantitative  determination  of  selenium  in  quinazoline 

18 


the  method  adapted  by  Becker  and  Meyer  was  found  to  be  quite 
satisfactory  (56).     Other  methods  are  listed  in  the  bibliography 

("). 

In  the  ultimate  analysis  of  carbon  and  hydrogen,  the  ordi- 
nary absolute  method  was  followed  with  the  use  of  copper 
oxide,  lead  chromate,  and  lead  peroxide  in  the  tube.  In  the 
determination  of  nitrogen  the  ordinary  absolute  method  was 
also  followed  excepting  that  a  considerable  quantity  of  specially 
prepared  lead  chromate  powder  was  mixed  with  the  sample  in 
a  number  six  porcelain  boat.  This  was  found  to  be  desirable 
when  the  dinitroselezazole  was  burned.  Selenium  dioxide,  which 
is  a  solid,  seems  to  be  formed  in  the  tube  and  carried  away  by  the 
current  of  carbon  dioxide  with  some  difficulty.  In  such  a  case  the 
analysis  usually  took  four  hours  after  the  combustion  had  actually 
started.  In  the  carbon  and  hydrogen  determination  selenium  dioxide 
was  easily  absorbed  in  the  presence  of  oxygen  gas. 

Preparation  of  2-Phenylbenzoselenazole 

The  first  method  employed  was  a  modification  of  the  method 
described  by  Fromm  and  Martin  (5S).  Method  (b)  is  an  adapta- 
tion of  the  method  for  preparing  benzothiazoles. 

(a)  Twenty  grams  of  benzanilide  was  mixed  in  a  pyrex 
flask  with  160  grams  of  selenium  dust  and  the  flask  placed  in  a 
nitrate  bath  under  an  air  condenser.  After  heating  for  an  hour 
at  220°  C.,  the  temperature  was  raised  to  250° C.,  and  kept  at 
250°-280°C.  for  sixteen  hours.  The  dark  mass  was  extracted 
with  hot  concentrated  HCl,  the  acid  extracts  filtered  through  glass 
wool  using  a  hot  water  funnel.  The  combined  extracts  were  poured 
into  a  large  volume  of  water  when  the  selenozole  precipitated  out 
immediately;  it  was  recrystallized  from  alcohol.  In  some  cases  it 
was  necessary  to  dissolve  in  hot  HCl  again  and  to  recrystalize.  The 
yield  was  twelve  per  cent. 

The  above  method  has  the  disadvantage  that  water  is 
formed  in  the  reaction  and  this  in  turn  reacts  upon  benzanilid 
at  the  higher  temperature  necessary  (as  selenium  only  melts  at 
217°C),  decomposing  the  benzanilid  into  aniline  and  benzoic  acid. 


H  ^ie 


/NHCOC6HS  /NH2 

CbH4  S  / 


Furthermore  benzanilid  boils  at  160°  C.  and  at  such  high  temper 
atures  as  250°  C.  and  over  some  of  it  is  apt  to  be  driven  off. 


19 


(b)  106  grams  of  benaldehyde  were  heated  with  93  grams  of 
redistilled  aniline  at  120°C.,  for  two  hours  or  until  the  solution 
was  clear.  The  clear  benzalaniline  was  then  poured  into  160 
grams  of  selenium  dust  in  a  pyrex  flask  on  a  sand  ba,th,  the  flask 
being  connected  with  an  air  condenser  as  before.  In  order  to 
distribute  the  flame  to  better  advantage  over  the  bath,  an  air 
space  was  made  between  the  Meker  burner  and  the  bath  by 
introducing  a  wire  gauze.  Hydrogen  selenide  was  evolved  freely. 
Complete  reaction  took  three  days.  The  extraction  and  recrystal- 
lization  were  the  same  as  in  the  former  case.  The  yield  was  sixty 
per  cent. 

The  selenazole  crystallizes  in  colorless  long  needles,  melting 
at  117.5°C.  (corr.)  Fromm  and  Martin  (58)  gave  the  melting- 
point  as  117°C.  It  is  insoluble  in  water,  and  in  the  following 
solvents  it  is  lightly  soluble  in  the  cold,  more  easily  hot:  ether, 
methyl  alcohol,  acetone,  acetic  acid,  acetic  anhydride,  chloroform, 
and  nitrobenzene.  It  is  difficulty  soluble  in  ethyl  alcohol,  ethyl  ace- 
tate, and  carbon  tetrachioride,  in  the  cold,  but  easily  soluble 
hot. 

Mononitro  Derivative 

The  mononitro  derivative  of  the  selenazole,  6-nitro-2- 
phenylbenzoselenazole,  was  prepared  by  nitration  with  nitric 
ncid  at  a  low  temperature: 

Twenty-five  grams  of  the  selenazole  were  dissolved  in  150 
grams  of  concentrated  sulphuric  acid,  keeping  the  temperature 
below  the  room  temperature  until  complete  solution  took  place. 
It  was  then  cooled  on  a  freezing  mixture  and  a  mixture  of  sul- 
phuric and  nitric  acids  (previously  prepared  and  cooled  by  mix- 
ing 9.5  grams  of  nitric  and  fifteen  grams  of  sulphuric  acids) 
slowly  dropped  into  it  in  the  course  of  half  an  hour,  using  mechani- 
cal stirring  for  four  hours.  The  solution  was  then  poured  into 
two  liters  of  water  (ice  water),  filtered,  dried,  and  recrystallized 
from  acetic  acid,  and  alcohol  with  the  help  of  animal  charcoal. 
The  yield  was  95  per  cent. 

This  nitro  compound  crystallizes  in  flattened  needles  of  a  light 
yellow  color.  It  melts  at  202.4°C.  (corr.).  It  is  very  insoluble 
in  water;  but  soluble  in  hot  acetic  acid,  acetic  anhydride,  nitro- 
benzene, nitrotoluene,  toluene,  benzene,  alcohol,  and  difficulty 
soluble  when  cold.  The  crystals  were  analyzed  and  gave  the 
following  results, 

Calculated  for  Found 

C..3H8N00,Se  I  II 

Nitrogen    9.24%  9.36%  9.48% 

Monoamino  Derivative 

The  conversion  of  mononitro  compound  to  6-amino-2- 
phenylbenzoselenazole  was  accomplished  by  the  action  of  tin  and 
hydrochloric  acid  as  follows : 

20 


30.3  grams  of  nitro  compound  were  mixed  with  42  grams 
of  twenty  mesh  tin  in  a  liter  flask,  immersing  the  latter  in  cold 
water.  175  cc.  of  cone.  HC1  were  slowly  added  to  the  flask. 
In  some  cases  it  was  necessary  to  apply  initial  heating  but  when 
once  the  reaction  started  it  took  place  rapidly.  After  the  effer- 
vescence had  abated,  the  flask  was  heated  over  a  free  flame,  under  a 
leturn  condenser,  for  two  hours.  The  solution  usually  turned 
to  a,  pasty  mass,  due  to  the  formation  of  a  tin  double  salt.  The 
mixture  was  dissolved  in  a  large  volume  of  water  and  heated 
on  a  water-bath,  the  precipitate  filtered  out,  washed,  and  pre- 
served. The  clear  filtrate  was  treated  with  concentrated  alkali, 
in  excess,  the  separated  amine  collected,  washed  with  water, 
dried  and  recrystallized  from  alcohol,  using  bone-black.  The 
precipitate  set  aside  was  treated  with  strong  alkali,  the  insolu- 
ble residue  washed,  recrystallized,  and  added  to  the  main 
product.  The  yield  was  75  per  cent. 

This  amine  crystallizes  from  alcohol  in  fine  yellowish  needles, 
melting  a,t  201.2°202.3°C  (corr.).  It  is  insoluble  in  water  and 
ether,  difficultly  soluble  in  the  hot;  and  fairly  soluble  in  aniline. 
A  pure  sample  was  analyzed  and  gave  the  following  results : 

Calculated  for  Found 

C13H10N2Se  I  II 

Nitrogen    10.25%  10.34%  10.42% 

Carbon 57.18  57.17  57.00       . 

Hydrogen   ....  3.69  3.79  3.85 

Decomposition  of  Monoamino  Derivative 

Five  grams  of  the  monoamino  compound  were  mixed  with 
powdered  KOfi,  heated  together  until  the  mixture  just  melted,  and 
maintained  in  that  state  for  a  few  minutes.  When  the  latter  had 
cooled  down  to  room  temperature,  cold  water  was  poured  over  the 
mixture.  The  filtered  solution  was  acidified  until  no  further 
precipitate  was  formed.  The  precipitate  was  collected  and  re- 
crystallized  from  water,  m.p.  121  °C. 

One  gram  of  this  solid  was  placed  in  a  test  tube,  provided 
with  a  cork  and  a  delivery  tube,  and  heated  with  soda  lime;  a 
liquid  with  the  smell  of  benzene  was  collected  in  another  test 
tube  cooled  with  water.  When  this  liquid  was  treated  with  a 
few  drops  of  nitric  acid  mixture  the  smell  of  nitrobenzene  was 
given  off.  A  gram  of  the  crystals  was  heated  with  concentrated 
sulphuric  acid  and  alcohol  when  the  odor  of  ethyl  benzoate  wa,s 
noted. 

Monacetyl  Derivative 

Five  grams  of  the  monoamino  selenazole  were  heated  on  a 
water-bath  with  10  cc.  of  acetic  anhydride  until  the  solution  was 
clear,  which  took  about  two  hours.  100  cc.  of  water  were  poured 
into  the  mixture,  which  was  then  neutralized  with  dilute  am- 

21 


monium   hydroxide.     The   precipitate   was   filtered,   decolorized 
by  animal  charcoal,  and  recrystallized  from  dilute  alcohol. 

The  acetyl  compound,  6-acetamino-2-phenylbenzoselena- 
zole,  forms  colorless  crystals,  melting  at  188.1°-.7°C.  (corr.).  It  is 
insoluble  in  ether,  benzene,  carbon  disulphide;  slightly  soluble  in 
toluene ;  soluble  in  alcohol,  ethyl  acetate,  amyl  acetate,  acetone, 
and  acetic  acid.  A  pure  sample  was  analyzed  and  gave  the 
following  result, 

Calculated  for  Found 

C15H12N2SeO 

Nitrogen    8.88%          8.92%     8.68% 

Mxmobenzylidene  Derivative 

Five  grams  of  the  monoamino  compound  were  dissolved  in 
200  cc.  absolute  alcohol  with  the  addition  of  3  cc.  of  benzaldehyde 
a,nd  the  clear  solution  was  boiled  on  a  water-bath,  with  a  return 
condenser,  for  two  hours.  After  the  solution  was  boneblacked, 
the  yellow  precipitate  was  recrystallized  from  carbon  disulphide. 
The  yield  was  90  per  cent. 

It  crystallizes  in  yellow  plates,  melting  at  156.7°-157.6°C., 
soluble  in  benzene,  ether,  ethyl  alcohol,  carbontetrachloride,  ace- 
tone, but  difficulty  soluble  in  ligroin.  An  analysis  of  the  crys- 
tals showed  the  following-  result, 

Calculated    for  Found 

C20H14N2Se 
Nitrogen    7.75%          7.92%     7.68% 

An  Azo  Dye 

Five  and  four  tenth  grams  of  the  monoamino  compound  were 
dissolved  in  hot  cone.  HiCl,  cooled  in  ice.  and  diazotized  with 
sodium  nitrite  solution,  until  starch  iodide  paper  showed  excess 
nitrous  acid.  The  diazotization  was  performed  in  ice,  with 
mechanical  stirring,  and  required  about  an  hour.  The  diazo  solu- 
tion was  poured  into  a  solution  of  3  grams  B-naphthol  in  8  ^rams 
of  NaOH  a,nd  60  cc.  of  water,  while  gradually  stirring.  A  very 
deep  red  solution  formed.  This  was  acidified  with  excess  HC1, 
salted  out  by  NaCl,  and  crystallized  from  aniline-alcohol  mixture. 
In  the  pure  state,  it  is  a  deep  red  powder,  with  a  metallic  lustre 
when  rubbed,  melting  at  284.2° C.  An  analysis  showed  the  fol- 
lowing result, 

Calculated  for  Found 

C28H15N8OSe 

Nitrogen    9.81%  9.75% 

Dinitro  Derivative 

The  nitration  for  the  production  of  dinitro  derivative  was 
at  first  carried  out  under  the  same  conditions  as  in  the  preparation 

22 


of  mononitro  compound  and  after  the  latter  was  formed  more  nitric 
acid  mixture  wa,s  added,  with  the  addition  of  heat : 
cone,  sulphuric  acid,  keeping  it  below  room  temperature.  It  was 
then  cooled  in  a  freezing  mixture  and  half  the  volume  of  a  nitric 
acid  mixture  (prepared  and  cooled  by  mixing  19  grams  of  nitric  and 
30  grams  of  sulphuric  acids  was  introduced  very  slowly  to  the 
selenazole  solution  through  a  dropping  funnel,  maintaining  at  this 
temperature  for  two  hours  (using  mechanical  stirring).  The  re- 
maining half  of  the  nitric  acid  mixture  was  then  slowly  introduced 
and  the  flask  was  heated  on  a  water-bath  for  two  hours.  The  solu- 
tion was  poured  into  two  liters  of  water,  the  precipitate  filtered  off, 
dried  and  recrystallized  several  times  from  acetic  acid.  The  yield 
was  80  per  cent. 

This  dinitro  compound  crystallizes  in  fine  yellow  needles, 
m.  p.,  246.8°C.  (corn),  very  insoluble  in  water,  but  soluble  in 
hot  acetic  acid,  acetic  anhydride,  nitrobenzene,  nitrotoluene. 
ethyl  alcohol,  and  difficultly  soluble  cold.  It  was  analyzed  and 
the  following  results  were  found, 

Calculated  for  Found 

C13H7N,O4Se  I  II 

Nitrogen 12.07%  12.30%  12.12% 


Diamino  Derivative 

The  conversion  of  the  dinitro  to  diamino  derivative  was  ac- 
complished in  the  same  manner  as  the  reduction  of  mononitro 
derivative  excepting  that  twice  a,s  much  tin  and  HC1  were  used. 

This  diamino  compound  crystalizes  in  yellowish  glistening 
needles  from  alcohol  and  pyridine;  m.  p.,  269°-270.5°C. ;  was 
analyzed  and  gave  the  following  results, 

Calculated  for  Found 

QaHuNsSe  I  II 

Nitrogen    14.6%  14.4  14.7 


Diacetyl  and  Dibenzylidene  Derivatives 

The  diacetyl  and  dibenzylidene  compounds  were  also  pre- 
pared from  this  diamino  derivatives.  The  former  crystalizes  in 
cubes  from  dilute  alcohol;  m.  p.,  307°C  (Corr.)  and  the  latter  in 
beautiful  yellow  plates  from  carbon  disulphide,  m.  p.,  195°-196°C. 
(Corr.).  An  analysis  of  these  two  compounds  showed  the  follow- 
ing results, 

Calc.  for  Calc.  for  Found 

C17H15N302Se      C27H19N3Se        I        II 
Nitrogen  ....  9.05%  11.21%     9.21%     11.43% 

23 


Dyeing  with  Azo  Dyes 

Both  the  monoamino  and  the  diamino  derivatives  form  in- 
tensely colored  dyes  when  diazotized  and  coupled  with  phenols 
and  aromatic  amines.  The  dyes  formed  are  fast  to  light.  In 
the  following  table  silk  is  given  to  represent  the  fabrics  used. 
Wool  and  cotton  were  dyed  similar  shades,  though  with  slight 
variation.  Each  silk  sample  was  dyed  in  a,cid  or  alkaline  baths  as 
indicated  and  each  bath  contained  0.01  gram  in  twenty  cc.  solution : 


Diazo. 


On 


Diazo. 


On 


Coupler 

1110110- 

amine 

silk 

diamine 

silk 

Phenol 

deep  red 

v.   light 

(alk) 

yellow 

(alk) 

yellow 

deep  red 

Dimethyl- 

orange 

light 

orange-red 

yellow 

aniline 

(acid) 

yellow 

(acid) 

P-nitrani- 

light 

brownish 

grayish 

iine 

brown 

(acid) 

brown 

(acid) 

P-tolui- 

light 

brownish 

brownish 

dine 

brown 

(acid) 

(acid) 

• 

Pyrogal- 

dark 

grayish 

dark 

grayish 

lic  acid 

brown 

brown 

(acid) 

(alk) 

Salicylic 

reddish 

light 

red 

brown 

acid 

(alk) 

brown 

(alk) 

B-naph- 

deep  red 

pink 

deep  red 

red 

thol 

(alk) 

(alk) 

Sulphani- 

light 

brownish 

brown 

brown 

lic  acid 

brown 

(alk) 

(alk) 

A-naph- 

light 

brownish 

yellow 

yellow 

thylamine 

brown 

(acid) 

(acid) 

Resor- 

purple 

red 

dark 

deep  red 

cinol 

(alk) 

purple 

(alk) 

24 


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37 


VITA 

Yii-Gwan  Chen  was  born  in  Nanking,  China,  March  8,  1893. 
After  graduation  from  college  in  1915,  he  further  studied  Chinese 
classics,  1915-16.  He  entered  Case  School  of  Applied  Science, 
Cleveland,  Ohio,  as  a  special  student  in  the  Department  of  Chemis- 
try, 1916-17.  He  registered  at  Columbia  University  to  pursue 
graduate  work  in  chemistry  under  the  Faculty  of  Pure  Science ;  and 
was  awarded  the  degree  of  Master  of  Arts  in  1918.  From  Septem- 
ber 1919  to  June  1922,  he  has  been  pursuing  research  in  organic 
chemistry  in  the  research  laboratories  of  Hlavemeyer  Hall,  Columbia 
University. 


28 


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